Method of chlorinating hydrocarbon mixtures



March 7, 1950 H. FLETT METHOD OF CHLORINATING HYDROCARBON IIXTURESv 3 Sheets-Sheet 1 Filed May 22, 1945 Z |...I p 6 E ff 4 ALT m r# m5. my wfg fmf e mx M www m W Ap. c afa. 2 ...l/4. fm n M l j ...nl .4 6/ wwz nrw 7 4 M 4 M AMarch 7, 1950 L H. FLr-:TT

.HETHOD OF Cl-ILORINTING HYDROCARBON HIXTURES 5 Sheets-Sheet 2 Filed lay 22, 1945 M m .E P

M m M March 7, 1,950

Filed May 22, 1945 l.. H. FLETT 2,499,578 METHOD QF CHLORINATING HYDRocARBoN mx'ruREs 3 Sheets-Sheet 3 OF//VE' Patented Mar. 7, 1950 METHOD F CHLORINATING AHsamocnRBoN MIXTURES .Lawrence H. Flett, Scarsdale, `N. Y., assignor to .Allied'Chemcal & Dye Corporation, Newl York,

Application May 22, 1945, Serial'No..595,-172

(CL G0-.505)

The present invention relates to improvements inthe method of chlorinating a hydrocarbonmixture of the type of a petroleum distillate.

It relates more particularly to improvements in the method of chlorinatingsuch hydrocarbon mixtures in connection with the manufacture of nuclearly substituted .aromatic sulfonates which are valuable detergents -apd wetting, emulsifying,.and .the like agents. One process for the manufacture of suchnuclearly substituted-aromatic -sulfonates involves .chlorinating .a .hydrocarbon mixture .of the type. of a .petroleum fdistillate; .condensing resulting .chlorinatedhydrocarbons with an aromatic compound with theaid of a condensation catalyst vof the vFriedel-'Crafts such as anhydrous aluminnmcliloride or anhydrous zinc chloride, toform a.,mixture. containing aromatic compoundshaving nuclear substituents; sulfonating a resulting mixture of nuclearly substituted .aromatic.compounds; andv recovering the resulting mixturenfsulfonic acida-.preferably in the form .of their. salts. .suchastheirsalts .with alkali -metals. The .invention relates particularly toimprovementsin the chlorination step of said .process whereby advantages .are secured in the manufacture of the mixtures .of nuclearly substituted aromatic sulfonates. nuclear substituents are .derived from hydrocarbon mixtures of the .type .of ,petroleum .distillates, and accordingly .are to a .considerable extent aliphatic acyclic and/or alicyclic in .nature, the nuclearly substituted aromatic sulfonates have .come to .be known in the .art Aas "alkyl aromatic .sulfonates`, the term alky being used in ageneric sense .to denote.a.nuclear substituent radical derivedfrom thehydrocarbon mixture. Accordingly, the nuclearly substituted aromatic compounds will be .referred to herein as "akyl aromatic compounds and-the term alkyl will he employed in said generic sense.)

.An object of the invention is to provide .improvements .in the chlorination of hydrocarbon mixtures of the 'type of Apetroleum .distillatea whereby mixtures `of chlorinated hydrocarbons are obtained .having a relatively low -aniline point. vitt is .a further object .of the invention to provideimprovementsin thestep ofthe above process in which the hydrocarbon mixture of the type of a petroleum distillate is chlorinated. whereby mixed alkylaromatic sulfonatespossessin'z excellent properties mayhe obtained inh'igh yields. (The term mixed is employed herein in .the sense .of hnixtures..") .morepmicobject of the invention is to provide improvements .in the. ...nf `the process .ot apre- (Since the paring mixed .alkyl .aromatic .sulfonates V,involving chlorinating .a paraiinic petroleum .hydrocarbon distillate. in .which .thehydrocarbons contain an average of .'lto 35 carbon atoms,.condens ing .resulting chlorinated hydrocarbons .viiith benzene, phenol, or naphtha1ene,.sulionating the resulting mixed. condensation lproduct, .and-.recovering the .mixedsulfonation product, ,preferably 'in the .form of an alkali metal salt; '.the improvements resulting .'in .products .of Llii'g'h quality which are obtained 1in excellent yields.

.Other objects of .theLinvention will jin parthe obvious and .wi11.in partappear hereinafter.

lIhe .mixed alkyl .aromatic slfonates whichthe present inventlonis particularly concerne'd are ,preferably derivatives of aromatic compounds o'f `the.benzene, naphthalene. .andiphenylseries. the products maybe derivatives .of benzene, naphthalene diphenyl, 'their homologs, `or substituted members of 'the series to which these compounds belong in which the substituents may be, for example, halogens or hydroxyl, aroxy, alkoxy,'lower alkylVor .carboxyl radicals which are present as nuclear ,substituents. Where the aromatic compounds are substituted, they preferably contain but -one sbsttuent. As suitable substituted aromatic compounds there may'be mentioned phenol, cresol, chlorbenzene, toluene, xylene, resorcinol, 'hydroxydiphenyl, phenetole, and salicylic acid.

As pointed out above, the alkyllgroups or sidechains present in thesulfonates are derived from ahydrocarbon mixture of the typeof apetroleum distillate; for example, a kerosene fraction or .a "white oil fraction of petroleum, or a Fischer- Tropsch reaction product. `preferably a distillate of -a vparafinic 4petroleum (that is, a distillate of a paraiiin-base petroleum).

In themanufacture of mixed alkyl aromatic sulfonateshaving .the desired type of alkylgroup and therefore having desirable properties, the manner in which the chlorination of the .hydrocarbon mixture is carried out is important. Reerences .'in 'the literature disclose that 'when chlorinatinga hydrocarbon mixture for .the purpose of nallyreplacing a hydrogen atom of .the hydrocarbon .molecules mithsome other radical suclras the hydroxylgroup, the bestyiel'ds of .the desired products are obtained when, at the .en'd of the .chlorination reaction, the amount of.organically .combined chlorine in the .chlorinated hydrocarbon -mixture .is -much Jess .than .that which...corresponds '.tn ne `atom `mi chlorine-,par moleculejthydmcarhon.

'.65 tbignaturamhiiiismmvergentlygtoanedmlmtes chlorination, should result in a high proportion or' desired products from hydrocarbon mixtures is also supported by theoretical considerations.

As is pointed out in my United States Patent No. 2,247,365, issued July 1, 1941, I have found, by chlorinating a hydrocarbon mixtureof the type of a petroleum distillate, such as a kerosene or white oil fraction of petroleum, and preferably a paraiiinic petroleum hydrocarbon distillate, to such an extent that the amount of chlorine which has become combined organically in the mixture is more than that which would be so combined if each hydrocarbon molecule present in the mixture were converted to its cor'- responding monochloride, that a chlorinated mixture is obtained which can be used successfully nate the hydrocarbon mixture to a degree not exceeding that corresponding with chlorination. 'Ihe actual amountpf chlorine intro- I duced relative to the amountl of hydrocarbon for the production of desirable mixed alkyl aro' matic sulfonates with exceptional surface-active properties, and that these sulfonates are obtainable in greatly increased yield, based on the amount of hydrocarbon mixture employed, than when an underchlorinated hyd'rocarbonmix-V ture is used. Hereinafter a chlorinated mixture containing an amount of organically combined chlorine which exceeds that which would be present if the mixture consisted of monochlorinated hydrocarbons only is said to be overchlorinated."

When a hydrocarbon mixture of the type'pf petroleum distillate is subjected to overchlorination by slowly introducing chlorine into a large amount of liquid hydrocarbonmixturentil the desired degree of chlorination is attained,^a oonsiderable period of time is required for the oper--` ation on a commercial scale. For example, 8 to 10 hours may be required for the overchlorinaf tion of a commercial batch of kerosene. If an attempt is made to reduce the period of chiari- A4 nation .by introducing the chlorine rapidly 'into the hydrocarbon mixture, a number of disadvantages result. Aside from the operating diiiiculties which result from the highly exothermic n a ture of the chlorination reaction, in some cases leading to flashing, a serious disadvantage is the marked lowering of the yield of mixtures of alkyl aromatic sulfonate obtained from the resulting' chlorinated hydrocarbon mixture. The disadvantages, furthermore, increase with increased chlorinaton temperatures. Thus I have found, when kerosene is overchlorinated -by passing chlorine,

in substantially the amount required for overchlorination, rapidly into the kerosene, the yield of chlorinated kerosene is substantially the same as the yield of chlorinated kerosene obtained by the slow introduction of chlorine, but the aniline point of the resulting rapidly chlorinated kerosene is generally much higher and the yield of alkyl aromatic sulfonate obtained from said rapidly chlorinated kerosene is much lower.

I believe an important difference in the result obtained lies in the fact that the rapid introduction of the total amount of chlorine required for overchlorination results in an uneven distribu tion of the chlorine among the various molecules of hydrocarbon, with the result that a relatively larger proportion of hydrocarbonmoleculesare left unchlorinated and a relatively larger proportion of the hydrocarbon molecules are polychlorinated than when chlorine is slowly intro` duced.

The present invention is based upon the discovery that chlorination of the hydrocarbon mixtures of the type herein denned can be eiected by the rapid introduction of chlorine into the hydrocarbon mixture in the liquid phase if` the chlorine is -iitioduced in portions ofthe'iuotar mixture will depend upon a number of factors, including intimacy of contact oi' the chlorine and liquid hydrocarbon mixture, and the chlorination temperature.

Without limiting the invention to any theoretical considerations, I believe the advantageous behavior of the hydrocarbon mixtures, when subjected to chlorination by the procedure of the present invention, in connection with the production of chlorinated hydrocarbon mixtures containing an amount of organically combined chlorine corresponding with at least chlorination, is related, at least in part, to the fact that the material subjected to the treatment is a mixure of hydrocarbons. some of which are more readily chlorinated than others. The chlorination of the more readily chlorinated components of the hydrocarbon mixture in a preliminary stage of the process, in'accordance with this in vention, seems to iniluencethe distribution of subsequently added chlorine favorably, as a result of which a greater proportion of the individual hydrocarbon molecules is chlorinated and a lesser proportion is left unchlorinated than when thetotal amount of chlorine necessary for effecting said degree of chlorination is introduced all at once. j

The process of the present invention may be carried out in various forms of apparatus. Thus the apparatus may include a plurality of separate chlorination units through which the hydrocarbon mixture to be chlorinated is passed in succession; it may include a single chlorination apparatus through which the hydrocarbon mixture to be chlorinated is repeatedly passed; it may include a single chamber provided with separate chlorine inlets spaced successively along the line of flow of the hydrocarbon mixture; or other forms which will be obvious to those skilled in the art.

It has been found that best results are obtained when the chlorination is divided up into two or more chlorination steps. After the preliminary chlorination to a limited degree, the next chlorination step may rapidly introduce the greatest proportion of the chlorine without disadvantageous results. When overchlorinating, it is advantageous to followby one or more additional introductions of lesser proportions of chlorine. To assure rapid reaction, the hydrocarbon mixture and chlorine are advantageously brought into immediate intimate contact. Preferably the chlorination is carried out in such manner that the vcessively introduced and caused to react with 75" "The`continuous procedure of the* the hydrocarbon mixture in said zones, so that the streamof hydrocarbon mixture reacts with successive portions of the total amount of ohiotine.

maintenance costs.- The `reducedisizeroffth'echlorinator makes it economically--feasible-:to: construct it from highly-corrosion-resistant-mmterialls,e.g;; glass or porcelain, which"-would'=be impractical for the 'largessizefequipmentfneeded for discontinuous batch chlorination;l Thecon-- tinuous chlorination-is easier =t lcontrolf.- This makesit possible to-producef a more-uniform product-.- Thef continuous chlorinator-can-be tted-with automatic labor-savingcontrol dea-- vices-with "obvious 'advantages 1 as -to cost''and'f qualityof 'the nalproduct; Due -to thefsmal amounts of material beingprocessed at -anyfgiv'enV instant,- hazards-due to ilre-are much lessa-with the continuous chlorinator: The continuous chlorinationprocess produces the hydrogen chloride, which is foxrnedas a byproduct ofthe chit rination-reaction; at f amore-constant;l stdierrate;4 thus "-facilitatingcits'- -recovery; e; g: as :anl aqueous solution ofuniform hydrogren` chloride content:

kfurther important Jadvantage ofi the present invention is the possibility2 ofcarrying outzfthef chlorination of petroleum hydrocarbon' fractions at temperatures above Athe ordinary temperatures;- e: g; at- '60 1:07200* C., with the Aattendant ad vantages of hightemperature operationf. and: without' certain disadvantages -inherentrinrbulk' chlorinatlonat such-highertemperatures.-A disadvantages are: decompositionreactins dura ing the chlorination-step,obj ectionabledarkcolor: of final alkyl aromatic sulfonate product; the dire hazard mentioned above which' becomeslfparti'cuiarlyacute at higher temperatures andxtreme difficulties in controlling flashing-and =deoompo sition.

'Ihe process of the present'inventionfhas the followingadditional advantages: The chlorinationl is easier to control, as theheat evolutionfduet chlorination occurs in aplurality ofreaction zones rather than in a single zone; there is lessdanger of excessive local overheating with Aattendant-delconroosition -of- -the hydrocarbons fand formation.' of soot. As a-conseouencei-operation at "higher temperatures is facilitated withvthe additional. benefits accruing from the use of the higher -terrb` peratures. In addition, continuouschlorinatiom ina plurality of zones has the advantage that'thef rate of kerosene ow can be mademuch greaterv4 with the result that -a muchgreater output canbe obtained fromthe chlorinatingf apparatus:

y For example, the maximum output of three in dividual chlorination units crmnected together inseries to give continuous chlorlnationin-a 'plurality'of zones is considerably greaterthan-thirstof 'the same three chlorination `units whenacnis operated Vseparately to obtain continuous chlo rnationin a Single step.

Itis advantageous to carry out "th'e chlorination of the hydrocarbon mixture, eachas akerosene or white oil" fraction of petroleum;A for the most part, and preferably-'for 'substantially-the entire chlorination period,A at a.- which is between'60 and F200" I' For the-chlO chlorination temperatures of about-:60? tod'? C: and preferably between 110 and 155%,-C., areenr ployed with advantage. The optimum chlorine.

tion temperature varies with-thehydrocarbon` aid of chlorinecarriers, catalysts, orsadjuvants;

such as;A for example, phosphorus*-trichloridm` iodine,- sunlight, e'tc. The extent and rate of chlorination ofthe-hydrocarbons can be controlled by means, such-as adjustment of the ratio of weights of chlorine and 'hydrocarbon mixturewhich intermingle in the reactingspace -in-a givenunit of time, and by stimulation-of the: reaction vby 4presence ln .the reacting. space ofi an carrier, catalyst or adjuvant. It isn-ot necessary in accordance with the present inventiomthat carriers, catalysts,'or adjuvants.- be employed; however. As-evident from of the following speciiic' examples, thefprooessfcan 'beeoper' ated cflicientlyv` infimes-dark and :in thez absence of added 'aduvants or carriers.'

The present invention may be .employedffor the, preparation of-v mixturesof- 'alkyliaromaticsul-- fonates wherein-'thefhydrocarbon-mixtureoffthe type of a I petroleumf distillateeis chlorinated to= various degrees. Thus. it mat' be*A employed in.4 connection with the-preparation' (1f-mixtures ofalkyl aromaticsulfonatcs in. which a.v petroleum distillateof the typeherein described-fis underchlorinated or is overchlorinated? that is in which: the petroleum distillate is chlorinated to anextent less thanperf-cent chlorination? or. greater" than 10021 per cent chlorination. `(Throughout this specication and the claims,- per cent chlorinationfis on a-molarf basis. It refers to the per cent'ratio between the actual increase in weight -due to chlorination of an` amount of hydrocarbon distillatecorrespondingtothe average molecular weight ofV thehydrocarbons in the distillate and thefexpectedfincrease in weight of the same amount and kind of hydrocarbon distillate if every'hydrocarbon in said amount of hydrocarbonv distillate were converted to its corresponding monochlor hydrocarbon. Thus, the per-cent :chlorination may be expressed by the formula:

where 34.5 represents the increase -in weight of anaverage molar quantity of hydrocarbon' mixture if all' the hydrocarbons in this quantityof mixture were converted to monochlor hydrocar-A bons only, and 'I represents'the actual4 "increase in weight of an average molar-quantity of carbon mixturcdue to. chlorine which is caused to become .organically combined; inthe. hydrn carbons of the quantity of mixture; by the chlorination) The present invention is of parthular advantage in connection 'with the chlorination of the hydrocarbon mixtures to a degreeeorresponding'to at least I5 percent chlorination; and and more particular-lytic a degree eomespondmg to more thanflllov per cent chlonlnationfbut duction-of such-fractions of petrolenmdistillatesg 76 these :limits it #is preferrcdmchlotuxatemiorhy-fdrocarbon mixture to a degree corresponding to not more than 175 per cent chlorination. Especially valuable results are obtained when the chlorination is carried out to a degree corresponding to between 110% and 150% chlorination, or more specifically to a degree corresponding to about 120% chlorination.

The hydrocarbon mixtures employed in the present process, such as petroleum distillate, are complex mixtures Whose composition is not deiinitely known. The approximate composition of petroleum distillates is determined by reference to the boiling points and the other physical properties of the compositions. Ordinarily, the petroleum distillates employed in the making of the alkyl aromatic compounds will boil over ranges the lower boiling points of which are not below 80 C. at atmospheric pressure, and the upper boiling points of which are not above 350.

C. at 22 mm. absolute pressure. For the manufacture of products designed for general detergent use, it is preferred to employ petroleum fractions which are derived from Pennsylvania, o r Mount Pleasant, Michigan, type petroleums and'which fractions boil for the most part over atemperature range lying between 180 and 300 C., and are preferably composed predominantly of open-chain and cyclic non-aromatic, nonolenic hydrocarbons which boil within the range 180 to 280 C. (It is Anoted that, where ranges are given throughout the specication and the claims, the-range includes the limits.)

While the process of the present invention is of particular value in connection with the production of alkyl aromatic sulfonates from chlorinated hydrocarbon mixtures of the type referred to above, the invention is not limited thereto, since it provides chlorinated hydrocarbon mixtures of low aniline point, which are valuable for the preparation of other products in view of the greater distribution of chlorine among the individual molecules of hydrocarbons in the mixtures. v

' The aniline point, mentioned above in connection with chlorinated hydrocarbon mixtures, refers to a determination made as follows: A chlorinated hydrocarbon material to be tested is freed from all traces of dissolved hydrogen chloride by bubbing a current of air through it for at least 10 minutes. 'I'hen in a dry test-tube a convenient volume, e. g., 5 ccs. of the aerated sample, is mixed with an equal volume of freshly distilled aniine. If necessary the mixture is warmed to obtain a clear homogeneous solution. While the solution is stirred with a thermometer it is cooled slowly and the temperature is noted at which the solution becomes so opaque, due to the development of turbidity, that Vthe bulb of the thermometer is no longer clearly visible. This temperature is known as the aniline point. I have found that the aniline point is a measure of the content of desired alkyl chlorides, presumably alkyl mono-chlorides, in chlorinated hydrocarbon mixtures of the type of petroleum distillates. Thus, two chlorinated kerosenes produced from the'v same'kerosene under different conditions but chlorinated to' the same degree, as evidenced by the same specic gravity, will lead to different yields of alkyl benzene sulfonates useful as detergents, if the aniline points of the chlorinated kerosenes are different, the higher yield of desirable alkyl benzene sulfonates generally being obtained from the chlorinated kerosene of the lgwerfaniline-point. In a typical determination @geanimeeraker-Qsenewere hlrinafeni und@ differing chlorination conditions until the increase in speciiic gravity due to chlorination was 0.1305 in each case. The aniline point of one chlorinated kerosene was 12.2 C.; that of the 5 other chlorinated kerosene was 37.0 C. When converted to keryl benzene sulfonates in the same: manner, the yield in grams of organic sulfonate per kilogram of kerosene subjected to chlorination was '751, in the case of the former, as compared with 453 in the case of the latter. A feature of the procedure of the present invention is the relatively low aniline points of the resulting chlorinated hydrocarbon mixtures.

The process of the present invention may be practiced in various ways. In general, a stream of hydrocarbon mixture of the type referred to above is passed in liquid phase through a chlorination chamber or zone, chlorine is introduced into the hydrocarbon mixture in said chamber or zone in an amount not exceeding that electlve to chlorinate the hydrocarbon mixture to a degree corresponding to A55% chlorination (and preferably not exceeding that effective to chlorinate to adegree corresponding to 35% chlorination) while in said zone, and additional chlorine is then introduced into a flowing stream of the resulting partially chlorinated hydrocarbon mixture while maintaining the temperature of the latter reaction mixture within the range 60 to 200? C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed in the chlorination being at least suiiicient to result in a chlorinated hydrocarbon mixture containing an amount of organically combined chlorine corresponding to 75% chlorination.

As a result of the chlorination, hydrogen chloride is formed. Further, unless extreme care and highly ecient operation are employed, the hydrogen chloride given off by the reaction mixture generally contains some chlorine. In addition, particularly at elevated chlorination temperatures, the lower boiling constituents of the hydrocarbon mixture and/or chlorinated hydrocarbons may, to some extent, appear in the exit gases. An Y advantageous method of practicing the present invention involves contacting or scrubbing the exit gases with the hydrocarbon mixture to be chlorinated. By coordinated regulation of the chlorine charged to the main chlorinators, the amount of chlorine in the exit gases from said chlorinators may be limited so that the amountl present in the exit gases does not exceed har. required to chlorinate the hydrocarbon mixture in the scrubber to the limited extent required by the present invention. Thus, the scrubber may be employed as the initial chlorinator inaccordance with the present invention and at the same time can serve to remove from the hydrogen chloride gas the vapors of hydrocarbons and/or hyo drocarbon chlorides as well as unreacted chlorine, which would reduce the utility of the hydrogen chloride.

To secure intimacy of contact between the liquid material being chlorinated and the ,0 chlorine gas, the chlorination chamber may be provided with packing material of various types.A

An advantageous method of securing intimate contact is to employ a high rate of ilow of the liquid hydrocarbon mixture to be chlorinated. By proper selectionof the size and shape of the chlorinating apparatus and the speed of ow of the liquid hydrocarbon mixture, the process may be operated under conditions of turbulent flow of the liquid hydrocarbon mixture in an unpacked 15 chlorlnatonmvessel or zone. An advantageous methode; oarri'lrle. out. thenrooeSs-involves-.passine the liquid hvdrooarbon'mixture throughl en unobstruotodohlorpatonaonewhich-lstereator length thea the eleotlve average width. of stream of liquid hydrocarbon.: mlggture, at a relatively, high averaeeveloolta (The elleotive everaaefwdthoi the streamla the averaeewldth. e,- al diameter., of. the .free seooef throueh-y whioli the etream. flowszthus.. of e eaokesl taboo? tower itis.: muohsmaller than tlleqeotual diameter of the tube or tower.) Preferably.: average velocity exceeds ofeet per. hourausl-nav bees hiehzaszo-Leetner hour. (operations at ever.- aee. velocitiesctfto 5;099 Ieetner hom'l oanbo readily carried out. (As employe@4 hex-.ehn the term average velocityfls thevvelooit! represented by thaequatlonf where A equals average velocity measuredrin feet per. hour; equals cublcfeetof liquid'per hour passing' throughf thechlorination.. zone; Lequals length infeet of the-.chlorination zone;-. andi- V5 equals volume -.cf f liquid hydrocarbon .mixturein the. chlorinationzone. at- .any instant, measured in foubicfeetL The particular average-- velocity employed in-.a giverrcase-will".dependuponother factors-of-the process, such as-intlmacy ofi contact between thellquid .hydrocarbon mixtureand'f the chlorine, theerate of chlorine now; .thetemperae ture of thechlorination, the degreet'cwhiclr` the chlorination' is fcarried out; and the nature offthe hydrocarbon mixture undergoing chlorination.- Thus for the chlorination nfapetroleumzdlstillate boiling-for-Ithemostpart-over artemperature range (at atmospheric pressure). lying;between- 180i'l and 3009' C.', whichhas been. givenarr-lnltial Achlcrlna-` tion to a degreenotexceding that corresponding with- 55%V chlorination and preferably.- not exa ceeding that correspondlngto-tt chlbrination, a-stream-of the-partiallychlbrinatedlhydrocarbon mixture inllquid phase maybe chlorinated: to a degree corresponding to-75%to 200% .chlorinaa tion by passing chlorine into said partially chloa rinated` hydrocarbon mixture-while thel latterv is owing at an average-velocity of'501tol0001feet. per hour and preferably-fromto 600 feet .per hour. The chlorination temperature is con-w trolled so as to-prevent-the-peaktemperature of the chlorination-fromexceeding 2009-0., and pref-.- erably l175" C; Qrdinarily-l in connection. with rapid now of the partially chlorlnatedhydrocarfbon mixture, the chlorination iscarried= outiatga teniperatre of' at least $0-'-G.'more particularly' atleast more andgrefergmyat least 1:10@ c.

In order thatv the invention may: be .undenstood' mores fully, referencershouldz b,6\had to the Iollowing examplesandthe accompanying draw?.

lasse in. v'vhienTub :Figo 1 is.aneievationeotonesformnfappanatus Fig. 2.is.an elevatlorr partlycinsection ofi an? other2 form of-fm" out. the chlorination;

,Fie'.. 3lis. a velevation. of; a. .modled form of. the chlorination in Eig;

als; ai; elevation part-la in4 ocation. of a modied form; oiolliallllaoh; shOWnJ-nnlga l.

'Eon-convenience, where akerosenc fraction.- or petroleum in thermes.. irl-.the examples; theproduct, obtainedL by." ohlorinatine atomica-*korst* 7o valve@ Iii product' obtained by' condensing the "keryP chloride with benzene, for example, is termed fkeryl" bzenzene. It'will be understood that the specic character-of the "keryl chlorides and kei-yl benzenes or other keryl aryl products will be dependent upon the particular kerosene used and the manner in which the process is oarried out.

The,.- appaiatus shown diagrammatically in Figi; lconsisted-.ofa chlorination chamber in the form of a: vertical tower or pipe I having an inlet 6- for the'. liquid hydrocarbon mixture or partially chlorinated hydrocarbon mixture, an inlet. 2 Aforl chlorine, and an outlet 3 for chlorinated kerosene and exit gases. The chamber I was enclosed' in a temperature-regulating jacket 5` through which cooling water or steam could be circulated to provide for regulation of the temperature in the chamber I. The apparatus included a second similarV chamber or tower H, having an. inlet Illfor chlorinated kerosene, an inlet I2 for' chlorine, and an outlet I3 for the chlorination reaction mixture. The outlet 3 from the chamber ortower I was connected with a separator 'I 4leading to an. outlet 23 for the gaseous pontion of the, reaction mixture (hydrogen chloridelcxcess chlorine and vapors of hydmcalbons. fand/or chlorinated hydrocarbons), andary-liquid duct Bvwhich was connected with the inlet I0 of the chamber or tower I I. A similai' separator I1 connecting. with the outlet i3 was provided for separating the gaseous portion of the.- chlorination. reaction. mixture into a gaseousf-.on vapor: V.por-tion, which was carried o tdimughloutl'etl'frand'a liquid portion comprising chlorinated. kerosene, which was withdrawn through-.duct .I.'8. A receiver I91 for the chlorinatedI `kemseizier was .connected to the duct I8 and was provided-withan outlet 25 for residual gases and vapors. 'Ihe outlets 23, 24 and 25 were connected to a header 26, which carried the gases and vapors into a scrubber 30 which was in'` the form ofa chamber or tower having an inlet 3| for hydrocarbon mixture and an outlet 3.2L. A separator 33was connected to the outlet 32 for separating the material flowing from the scmlbber into 2, gSous portion, which was removed through an outlet 36, and a liquid portion (partially chlorinated hydrocarbon mixture) which was carriedby a pipe 34 to the inlet 6 of the chamber or tower, I. .Valves 40 and 4I were provided; in thefsupplyline 45, for hydrocarbon mix,- tlire whereby the hydrocarbon mixture Could .be latrodlloodf ietooither or both of the tower I @43d- Solllbber: 3 0, ,as desired, Thermometers alla 4.4 were provided for measuring the tem.- perature of the chlorination, reaction mixtures Loayingthezehlorinationohambers I and IfI., and additional-thermometers; 8. 2Q, 3l. and 38 were provided. for .measurwa-thc. temperature of. the material. honing; through. system at the pointfllldlgatedun-.Fia l of the: draw-ing;

means were providedfor securing in: timate; contact or chlorine. introduced into taechamberslonztcwens- I; and I-I through inlets 2 and I2, withthe. liquid; introducedvthrpugh in.-A Iets 6 and l0. includedaporous Alundum disc 0r a having a multiplicity of smallxholes closed end thereof.

In operating apnarabas. a.. streamer lm -of the. type above referred toivaslntroduoedfinto-the-tower I and allowedto nog over. intonaco-.I1 and on. through, the. duct I into.-I1he receiver L9; .out through .open

f ai blol'ue. were.

11 into the towers I and II through inlets 2 and I2 which were controlled by suitable valves. Cooling water was circulated through the jackets 5 and I5. The scrubber 30 was lled' with kerosene and valve 40 was closed.

After a short time, excess chlorine and hydrogen chloride gases given oi by the chlorination taking place in chambers I and II were passed into the scrubber 30, the valve 40 was opened and the valve 4I was closed. The flow of hydrocarbon mixture through the inlet 3| of the scrubber 30 and the flow of chlorine through the inlets 2 and I2 were adjusted so as to have excess chlorine in the gases entering the scrubber 30 through header 26 and inlet 35, but in an amount insuiiicient to chlorinate the hydrocarbon mixturefduring its passage through the scrubber to a degree higher than that corresponding with 55% chlorination By adjustment of the rates of chlorine streams introduced through inlets 2 and I2 the partially chlorinated kerosene entering the towers or chambers I and II was further chlorinated to an ultimate degree such that the chlorinated kerosene passing into receiver I9 contained an amount of organically combined chlorine corresponding with substantially 120% chlorination. When this state was reached, valve 46 was adjusted to collect chlorinated hydrocarbon in receiver I5, from which it was drawn oi at intervals.

Erample 1 0 F. Initial boiling point 366 5% vdistilled 378 10% distilled 387 50% distilled 432 90% distilled 496 95% distilled 516 Maximum distillation temperature 538 The specific embodiment of the apparatus included water-cooled towers I and II, each constructed of a Pyrex glass pipe 4 feet long and 2 inches in diameter, which were packed with 1/2 inch porcelain Berl-saddle packing material; and a scrubber 30 constructed of a Pyrex glass pipe 4 feet long and 3 inches in diameter, which contained no packing material and was cooled by contact with the atmosphere.

Operation was started inthe manner described above, the temperature at the tcp of towers l and II, as shown by thermometers 4 and I4. was allowed to rise to about 100 C. When the scrubber 30 and towers Land II were operating, the kerosene rate of iiow into scrubber 30 was set at 41 pounds per hour.; The chlorine was introduced in gas form under a gage pressure of about 25 pounds per square inch. The chlorine-rate of input through inlets 2 and I2 was adjusted until kei-yl chloride of a.- specliic gravity of 0.918 was obtained in receiver I9 (corresponding with about 120 per cent chlorination of the kerosene), and partially chlorinated kerosene of a specific gravity of 0.793 (corresponding with about 4.6 per cent chlorination 'of the kerosene) was discharged from the scrubber 30 into tower I. The keryl chloride discharged from tower linto tower II 1.2 had a specific gravity of 0.882 (corresponding with about 81 per cent chlorination). By adjustment of the cooling water in jackets 5 and l5, the temperatures at the tops of the towers were held at about 110 C.

Continuous operation of the apparatus was then carried out in this manner with steady production of keryl chloride of about 0.918 specific grav'- ity and having an anilinepoint of 7.5 C. The average velocity of the liquid passing through tower I was 85 feet per hour. For determination of the yield of keryl benzene sulfonate obtainable from the resulting keryl chloride, a portion of it was subjected to the following treatment: Five hundred parts of the keryl chloride were added to an agitated mixture of 1,000 parts of benzene and 25 parts of anhydrous aluminum chloride. (Parts, wherever indicated herein, are by weight unless specied otherwise.) The mixture was heated to 45 C., and held at 45 C. to 50 C. for about a half hour. The resulting condensation reaction mixture Was allowed to stand over night (16 hours) and the oily upper layer was separated from the tarry bottom layer. The separated oily layer was fractionally distilled to remove excess benzene, rst at atmospheric pressure and then at reduced pressure (up to 85 C. at 30-50 mm. pressure). The pressure was then adjusted to 5 mm. of mercury and a small fraction' of distillate boiling up to C. was collected and saved as recovered kerosene." Distillaticn was then continued with recovery of all material boiling between 95 and 235 C. at 5 mm. pressure; it consisted essentially of keryl benzene. The resulting keryl benzene was rened and sul fonated in the following manner: A -gram portion of the keryl benzene wasstirred with 10 ccs. of 100 per cent sulfric acid, heated to 40 C., and agitated at 35 to 45 C. for a half hour. The resulting mixture Was transferred to a separatory funnel, allowed to stand for a half hour, and the separated lower, colored acid layer was drawn ofi and discarded. The upper, rened keryl benzene layer was then placed in a glass sulfonating ask and 140 grams of 100 per cent sulfric acid was added with agitation. Sulfonation of the keryl benzene was completed by warming the mixture to 55 to 60 C. and maintaining the agitated mass at the temperature for about one hour. The sulfonation reaction mixture was'then run into 200 cc. of Water while simultaneously adding suicient 25 per centsodiuml hydroxide solutionto maintain the mass substantially neutral to phenolphthalein. The sointion was then brought to substantial neutrality (light green on nitrazine yellow paper) by necessary additions of sulfricacid or sodium hydroxide solutions. The neutral slurry was analyzed as follows: a; 10 cc. portion of the neutral slurry was transferred to a tared beaker, weighed, and evaporated (at tov135 C.) to constant-weight.. From the weight ofthe dry sample, the total solids present in the slurry was calculated. --The sodiumkeryl benzene sulfonatecontent of the solids was determined -by dissolvingr in 10 ccs.; of distilledl water a one-gram sample of a drum-dried sample; of theslurry; adding 100 ccs. of anhydrous ethyl alcohol; stirring.; :letting `the mixture stand-:for 15 to 30 minutes; collecting the insoluble inorganic salts on a tared Gooch crucible; washing with several small portions of anhydrous ethyl alcohol; drying at 105 to 135 C.; and igniting at 600.910.700 C. for half an hour. The dileramassed?.

ence between the resulting weightof the salts.v and the weight of the sample was the Iweight oll sodium keryl benzene sulfonate in the sample. Therefrom, the proportion of sodium keryl benzene sulfonate in the slurry was readily calculated.

The yield of sodium keryl benzene sulonate produced from the chlorinated kerosene obtained in accordance with this example, when determined in this manner, was 855 grams per kilogram of kerosene. The product had excellent color, wetting power, and detergency.

As noted above, the chlorination process of the present invention may be carried out in otherv types of apparatus. For example, I may chlorinate -a petroleum distillate to a limited extent by using the device shown in Fig.` 2 and then attain the desired higher degree of chlorination byv using the said device to contact the partially, chlorinated petroleum distillate one or more additional times with chlorine gas. The degree of chlorination attained on each passage of the hydrocarbon .fraction through the apparatus, in this case. depends to a large degree on the relative rates of flow of the hydrocarbon material and of the chlorine. Slower rates of chlorine flow will, other things being equal, reduce the degree of chlorination attained on contacting once with the hydrocarbon stream.

For countercurrent iiow, the apparatus of Fig.. 2 was operated as follows: Kerosene was introduced through a valved glass tube H3 into the top of a glass column H4. The column was. not packed but was provided with numerous indentations to insure thorough mixing of the reacting streams. Valve Hl in a tube H6 connected to a iiask H2 communicating with theA column H4 w-as closed. The kerosene was maintained in the flask at the level shownby the line- H5.` The kerosene passed down the column ill-.contacting an upward stream of chlorine gas which,- in=the form-of ne bubbles, entered the reocton zone through a ber glass sintered lter Hl. The chlorinated kerosene was drawn off through-valved tube l I8 while the hydrogen chloride prodvcad in the reaction was drawn off through the gas exit H 9. Cooling water was passed through a jacket l2 to control the reaction temperature which was measured by a thermorneter |21.

In carrying out a chlorination, the column-was rst led three-fourths full' of kerosene,v and:v chlorine passed in until the kerosene had reached thedesired degree of chlorination. During this periodfthe apparatus was warmed up to the desired"tmoerture (86 to 85.5 0.)'. The ow-o' kerosene' into the apparatus through ltube i i3 and withdrawal of chlorinated product through outlet H8f-were-then started.' The flow of cooling waterthrough the jacket 23 was adjusted so that the thermometer l2! indicated a temperature QL about86" C. After starting the flow of keroseneendmaking adjustments of temperature, now ofV chlorine, etc., the product was discarded for atime (about minutes)V until it was-felt that-a; stableI state of conditions had been attained.; Thereafter, chlorinated 1 kerosene lwasA collected;

E01. concurrent flow. the apparatus; of;Eig,x2; was oper-ated as follows: Kerosene enteredthe'; device through the valved tube H8.a nd chlorinatedkerosene was drawn off through-tube-l I6.. The-:valve in tube H3l was kept Aclosed and the: hydrogen chloride produced by the reaction wasdrawn ogtbrouh the .elntubeilla The .emu-l ist* rine gas enteredthrough the `berV glass-sintend, lter H1.

In carrying out the concurrent chlorinationfofv the kerosenathe column H4. was filled with the kerosene up to-a shortrdistance below its junction with the-flask, and chlorine was passed in until the kerosene had reached the desired degree ofchlorination. During this period, the apparatus was allowed to warm up to the desired temperature. The ow of kerosene into the apparatusA and out, in chlorinated form, was-thenbegun; The flowof cooling water through the jacket' |20 was adjusted so that the thermometer |2I indicated the desiredv temperature. After 4starting the kerosene ilow and making adjustments of temperature, chlorine flow, etc., the product was discarded for a time until it was feltl that a stable state of conditions had been-attained; The chlorinated kerosene was thenn co1- d .lected.

The followingv example illustrates-the use of the apparatus shownV in Fig. 2 in this manner,- employing countercurrent flow:

Example 2 The -A kerosene used in this example was th same `as that used inExample 1.

The column H4 was filled with the kerosene up to-a short distance below the-flask H2 and chlorinewas passed in at the rate of about 3.6 lgrams per-minute for about A5 minutes. The temperature was allowed -to rise to 60to 70 C; The flow of-kerosene into the apparatus through tube H3 andfwithdrawal ofchlorinated product through .tube Hfwere then started. The rate of liquidflowthrough the--columnvwas adjusted so that approximately 18 grams of chlorinated kerosenewere obtained during Aone minute. The-diameterof tube-1 I4 was 2' om. The eifective/cross-section ofA` thekerosene stream wasabout 95% ofthel actual cross-sectional area. The average velocity wasaccordinglyabout 12.3 feet per hour. The rateof chlorine now was maintained at about 3,-6 grams per minute. The ilow of cooling Water through the jacket was adjusted so that the thermometer-HI indicated a temperature of 60' to 70 C. Therst 200 cc. of product were discarded during stabilization of conditions. Thereafter, a 3885 gram portion of chlorinated kerosene having a specific gravity of 0.8440 (corresponding with about-52% chlorination) and an-aniline4 point of 49.5' C; was collected.

This chlorinated kerosene product 'was stored" in aloosely stoppered askfor about 20 hours'- and then further chlorinated using the sameigeneral'procedure asbefore. The chlorinated prod'- uct` wascollected at the rate-of-about 15- gramsh per minute; In' order -tomaintain* thech1orina--. tion reaction at#4 approximately the desired temthroughthej acketf. The temperature regis-'-P tez-ed by thermometer- 2 I was about 40"'to 50 'Cs whilev the eluen-t productffhadl af *temperature-o1l C. About 3550 gramsjofachlorinated prodi uct-ofispecicgravity 018824 (corresponding withv about; 81%" chlorination) and having `al1-.2111111x195;V

jacket I for about 15 minutes to warm up the apparatus. The steam was then shut oi. The heat of the chlorination reaction wassuicient to maintain a suitable temperature which registered as about 55 C. on the thermometer 2|. The product obtained when operating under these conditions had a specific gravity of 0.9246 (corresponding with about 125% chlorination) andan aniline point of 7 C.

A portion of the chlorinated kerosene was condensed with benzene in the following manner: 608 grams of benzene and 15.2 grams of anhydrous aluminum chloride were agitated. at room temperature in a glass flask and 304 grams of chlorinated kerosene (prepared as described above) were run .in during the course of 20 minutes. The reaction mixture was warmed to and agitated at 44 to 46 for an hour and a half. After allowing the mixture to stand about 16 hours, the lower tarry layer was separated by decantation and discarded. The remaining crude reaction product was distilled, rst at atmospheric pressure to remove unreacted benzene, and then under reduced pressure. The fraction boiling from 80 C. at 4 mm. of

mercury up to 255 C. at 20 mm. of mercury,

fined and sulfonated in the following manner' 100 grams of the distilled condensation product were agitated at room temperature for about three-quarters of an hour with 10'cc. of 100 per cent sulfuric acid. After standing for about half an hour, the acid layer was drawn oi and discarded. The refined oily material was then agitated and sulfonated by adding 100 cc. of 100 per cent sulfuric acid at room temperature over a period of 10 to 20 minutes, and then warming the mass to to 60 C. andv agitating for one hour. After adding l cc. of water to the 'sulfona tion mixture and agitating briefly, the mass was allowed to stratify for one hour. Three layers formed. The intermediate sulfonic acid layer was separated from the upper unsulfonated oil layer and the lower spent acid layer. ionic acid layer was poured onto about 500 grams of cracked ice and the resulting solution was neutralized by adding 93 cc. of 50 per cent aqueous caustic soda. Sufficient sodium sulfate (anhydrous) was dissolved in the neutralized so1u tion to bring the inorganic salt contentiof the solute up to about per cent. The solution was then dried on a double drum drier to obtain a iiaky product having excellentdetergency and wetting power. The process of this example produced 784 grams of organic detergent mate rial per kilogram of kerosene consumed.

Stepwise continuous chlorination may alsogbe carried out ina modiedform of the apparatus of Fig. 2 which is shown in Fig. 3. This involves a modified column -H4' containing a. plurality of spaced chlorine diiusers IIT', I II", and II'I".' whereby several streams of, chlorine are con4 tacted successively with a stream or kerosene or other petroleum hydrocarbon mixture. In th"peraton` of the modified apparatus., kero-' sene (for example) is introduced in a .continuous stream into the bottom of the column IM'; as the kerosene flows upward through the column, it comes in contact successively with three inde: pendent streams of chlorine gas entering through ber glass sintered` diffusers- I I7', III", and II`I". The chlorinated hydrocarbon material ilsepaxatedtrom hydrogenchlorde and. any un:

The suloutlet Ils contanedaboutSF-.of-chlorine. Thereacted chlorine in the iiask II 2. The chldf rinated hydrocarbon product is drawn if through outlet H6 while the gases pass out through the tube IIS. As required, heating or cooling means (not shown) are used to aid in maintaining the temperature of the column within the desired temperature limits, depending upon the chlorination temperature and rate of flow of the reaction mixture through the apparatus.

Example' 3 A mixture of kerosene of the type employed lin Example 1 and recovered kerosene derived therefrom, containing 79 per cent of kerosene and 21 per cent recovered kerosene, was chlorinated in an apparatus of the type shown in Fig. 3 to which a combined initial chlorinator and scrubber for the gases (similar to scrubber 30 of Fig. 1) was attached. The specific embodiment of the chamber IIII was in the form of a nickel tube 8 feet long and 4 inches in diameter provided with a chlorine inlet II I at the bottom, a second chlorine inlet II'I" spaced 171/2v inches above .inlet I I1', and a third chlorine inlet I I'T'" spaced 161/2 inches above the second inlet. It was packed with 1A inch porcelain Berl saddles and was surrounded throughout its length by a series lof three separate cooling jackets. For measurement of temperatures, thermocouple's'were inserted at spaced intervals along the length of the tube. 'Ihe scrubber 30 consisted of a VPyrex glass tube 4 feet long and 4 inches in diameter which was enclosed in a steel temprature-regulating jacket through which -v water or steam could be circulated. The outlet IIS was connected to inlet 35 of the scrubber and the inlet II8 was connected to pipe 34 and valve 4I by duct 48. The scrubber 30 was also packed with 1A inch porcelain Berl saddles.

In the operation of the apparatus, the kerosene mixture (having a specic gravity of 0.788) was preheated to 135 C. and pumped into tube IUI through the line 45, duct 48 and tube I I8. When the Vtube II4 was filled, chlorine was started in through inlet I I1 and then through inlets II'I and II'I'". When the keryl chloride leaving the chlorinator through exit line IIS had a specific gravity of about 0.900, the kerosene flow was gradually diverted to the scrubber 30, and after the scrubber 30 was in operation and liquid from the scrubber 30 was owing through the pipe 34, valve 4I was shut and the kerosene mixture was then in troduced into the system" solely through inlet 3|. By vcontrol of the chlorine introduced into the separate inlets I I1', I I'I", and I II'", and by suit-v able control of the cooling water in the jackets surrounding the chamber II4' the temperature was maintained within the desired range. as shown by the thermocouples. After equilibrium had been established, the operation of the appa. ratus was continued in the following mannerz'. The kerosene mixture was introduced into theI scrubber Aat a temperature of about C. and at the rate of 183 pounds per hour. Chlorinewas introduced through the inlet II'I at the rate of 38.5 pounds per hour, chlorine was introduced through the inlet II1" at the rate of 18 poundsA per hour, and chlorine was introduced through the inlet I'II'" at the rate of v18.5 pounds per hour. The 'temperature of the partially chlorinl' ated kerosene entering the tube III' was about 84 C. and its specic gravity was 0.798 (corresponding with about 10% chlorination). The gases leaving the chlorination chamber through 2mal-tvs 17 vrag velocity J"cf the ilidui'd passing 'through the tube 1M was 178 feetperfhour. The tempeatur'e's'at 1VariOuspoints within the -tub'e |14', recorded by the thermo'couples, were as -set out in "the following -ta'rle:

The "ke'ryl vchloride "continuously l'produce'd in this manner had aspecicgravity of 0.919. For determination of --the yield of keryl benzene sulfonate obtainefdfror'n said keryl chloride a portion of itiwassubject'ed to the treatment described in Example 11. The yield of sodium'keryl benzene sulfonate thusobtained was 858 grams per kilogram of kerosenefmixture subjected `to -chlorinatil.

Additional apparatus'fr carrying 'out' stepwise continuons enlonhatinisuisisedinlrigfi. 'It cis'istsisfsentlallyfo'fa ,plurality of t"chloi-inati'o'r1 chambers |30, "|131, fand |32 fhavin'ghi'cans for iiwing La stream "'of liydrocarbo'n,A rsuchjas kerosene or white oil, jsuccessiiely through `"theiri means for l"sepaat'ely .introducing -a stream of chlorine 'gas i'ntb *each "chlorination Jcl 1arb"er (showhfas'cpillaiy ytubes i|36, 31,-an'd |38) l"and irleans 2for `re'nio'i'firfi-,f the chlorination products from tli'e Iapparaltus (sho'wn as discharge 14|). outlets fld'z, 4453 'and fm for hydrogen chloride and "'resid'ual `cl'ilo'rlne "are "provided -Agitators |46, lid'l', and V|413ai'efalso 'pryided'ftoincrease'fthe c'o'n a't 1net ui'ele'n'the 'hydrocarbon 'niixturez 'and chlorine. The rratetf "chlorine iow -is -regulate`d by suitable devices (not shown). The rate of chlorine ow is not necessarily the same through all the various inlet tubes. The apparatus may be heated or cooled, as required, by any suitable'temperature regulating means (not shown). `llhe temperature may be varied from one chlorination zone to the next by suitable choice of the heating or cooling means.

The following examples illustrate the operation of the type of apparatus shown in Fig. 4:

Example 4 Kerosene having a specic gravity of 0.788 'at 24 C., and a boiling range such that over 80% distilled within the range 194 to 256 C. withthe 50% distillation point about 220 C., was `flst ltere'd through .-vltercel f (a -diato'm'aceous fearth product) andf-then" was run'f intofglass vrchambers |30, 3| ,fand"|3 2,ieach'of about one liter capacity andl exposedr-to--diiuse'd daylight, -un-til -the'overow level was reached in each (aboutfhalf full). Th ekerosene lratewasthenadjusted so that fthe rate'ofinput (tube |34) andl output (tube |4I) flow wasabout-GG-ccs.' per minute. The chlorine input through tubes-|36, |31 and IBS-.was then adjusted .-so-thattherate was-5 to (Segrams of chlorineper minute'-x'ito cna'mber ='Al1`three chambers were'coled somewhat'thetemprature being kept vat about =97 to 105 C. in chambers |30 and |3| and about 100 to 108 C. in chamber |32. The chlorine-used was purified by vbubbling through concentrated sulfuric acid. After operating for about an hour, steady state conditions were established. About 500 grams of chlorinated kerosene were then collected. This`chlorinated kerosene had adensity of 0.918 4at 24 C. (corresponding with about 120% chlorination) and an aniline point of '8.5 C. The-partially' chlorinated material flowing through tubes |42 and |43had densities of'about 0.829 and 0.859, lrespectively (corresponding with about `40% and,64% chlorination, respectively) ,after steady state .conditions had been reached.

Example '5 4Kerosene of the type employed inExample 4 was chlorinated at different temperatures :fin apparatus of the type shown'in Fig. .21, rin the presence of diffused daylight, b y a procedure substantially like that described in AExample 4, but differing 'therefrom .in the following particulars: The uniform kerosene rate Was fadjusted so 'that theinput (tube Y|341) -.and-.output (tube 4|) flow was-about 41'ec..per minuteyathe chlorine input through the tubes |36, -IGT :and |38 was adjusted so :that therra-tewas 3 to 4 grams chlorine s per .minute `into chambers |30 and vISL'fand'abOut- 'to '7 gramsichlorineper minute into .chamber -|32. ZWhen fthe lspecific gravity (determined at 24 C.) ofthe nalchlorinated material had increased to'.0.915 `,to .0.922. the` vcl'rlorinationwais considered finished. Chlor-inations-were madefat=60 to.-.61\C., 62 to .105 C.,'99lt0 101 C., '102=to 105'.C.,:100`t05121-'C., 110 to 145 C., vand .114 `to :1802C.

Each of these .batches pf rchlorinated kerosene was condensed with benzene 'in 'the "following way: -608 grams of benzene -and 15.2 .gramseof anhydrous aluminum chloride 'were pl-acedin'a glass-flask andstirred. -304 gramsof the chlorinated kerosene 'were :then l'run -in at room *temperature during the course'of 20 fminutes. The

Y temperature was then raised to 45 C. in5\,min

utes and held at 44 to .46 C. for an .-hour and a half. The reaction mixture was then allowed to stand about 16 hours. The tar which separated out was ldrawn o and discarded. The remaining crudecond-ensation product was then distilled by heating it to 100=C.=at.ordinary pressure to strip itof'most of'the unreacted benzene; then, to insureabsence of substantial amounts of. benzene frornfthe desiredkerylbenze-ne fraction, the stripping was'con'tinued by reducing the pressure in the stillfirst-to 40- mrn.- andfinally to '4 mm. of 'mercuryv absoluteipressurewhile thev temperature during Vthis phase was -allowed to drop somewhat, the final temperature being aboutv C. After'this pointf-the distillate which came over betweenfll" and 238 C.=a't 4 mm. mercury pressure was collected as the desired keryl ben- "Zene fraction.

The several keryl'fbenzenes -thusprepared from the same kerosene by chlorination at .different temperatures were 1- next refinedfand-esulfonated as follows: grams of an aikylbenzene sample were agitated for three quarters of anihourat room temperature with 10 cc. of 100 percent sulfuric acid. After allowing the -mixture to stand for 30 minutes, thedark-colored sacidlayer was drawn olf and discarded. The rnedoil was then sulfonated by agitating it with '76 cc. of 100.per cent sulfuric acid for 1 hourfat,55 to 60 C. The'sulfonationmass'was'then'al 19 lowed to stratify for about 1 hour. Three layers formed. The intermediate sulfonic acid layer was separated from the upper unsulfonated oil layer and from the lower spent acid layer, diluted with about 400 cc. ice, and neutralized with 50 per cent aqueous caustic soda.

In each case, the yield in grams of organic sulfonate in the resulting neutralized solution was determined in the following way: An aliquot portion of the neutralized solution was evaporated to dryness and the residue weighed, using quantitative precautions. The total solids content of the neutralized detergent solution was then calculated. A one gram portion of the desired solids was dissolved in ccs. of water and the inorganic salt was precipitated with 100 ccs. of anhydrous alcohol. The inorganic salt was collected in a Gooch crucible, and was washed with a little anhydrous alcohol, thereafter dried and weighed. The alcohol-soluble material was substantially all sodium keryl benzene sulfonate, and its yield was then readily computed. Sunicient sodium sulfate was then dissolved in each of the neutralized solutions to adjust the inorganic salt content of the solute to about 60 per cent. Each solution was then dried on a doubledrum drier.

Each of the light-colored iiaky products so obtained had excellent detergent properties. These keryl benzene sulfonate compositions were also compared for odor in the following manner: A 5-gram sample of a freshly dried composition was weighed out in a tall-form, 600 cc. glass beaker; to 30 cc. of hot distilled water (90 to 95 C.) were poured onto the sample, and immediately thereafter the degree of unpleasant odor of the vapors from the solution was noted. A sample which was substantially devoid of odor was rated good; samples having unpleasant odors were rated according to increasing odor: "fairly good, fairf and poorf The data obtained are reported in Table 1I. The favorable eiect of temperatures of chlorination from about 100 to about 120 C. on yield' of sodium keryl benzene sulfonate and on odor of the Iinal sulfonate composition is definite and surprising.

terial in the'bottle was noted at specied inter. vals; for example, every 24 hours. For comparative purposesa similar test was applied to a sodium keryl benzene sulfonate composition which was prepared from chlorinated kerosene prepared y by a batch chlorination. The results of this aging test are shown in Table III:

Table vIII Odor Noted at End of Test Period Tested Period in j-Product of Run No. v

Days Slight odor` Do. Very slight odor.

Slight odor. Very slight odor.

slight dor. Strong odor. Extremely strong odor.

Batch chlorination -It will be evident tothose skilled in the art that the inventionis not limited to the details of the foregoing illustrative examples and that changes can be made without departing from the scope of the invention.

The devices illustrated in the attached drawings-are meant to illustrate various suitable apparatus for carrying out the chlorination of hydrocarbon mixtures in accordance with the present invention. No limitation as to the scope of the invention with regard to chlorination devices is to be deduced therefrom, however. Further, it is not intended to restrict the scope of the invention to chlorination devices made of any specic material. Other materials of construction Table II Temperatures Yield of Specitlc Keryl Ben Odor (Rated Run Cghriv'iilxtly ggd zene (SulfofgroFreIgdom o a na e' g. per m ero- No' 553g() Salusl ga Kerogee at KKilo of sono like (sa) (so.) (no.) 24 Cosrsr) Odor) 60 61 0. 917 722 Poor. 62 62 0. 916 749 Fairly good 99 101 100 0. 921 790 D0. 105 102 102 0. 916 798 D0. 100 120 121 0. 914 814 G 144 145 0. 910 749 'DJ 114 177 180 0. 916 763 D0.1

l These products, although free trom kerosene-like odor, had a. dlenent, musty odor. As shown in Table II, only one, or none, of resistantto chlorine and hydrochloric acid may the three chlorlnating ilasks in each of the runs #'1, #2, #6 and #7 was maintained at a temperature between about 100 and about 120 C., and in these runs, the yields of keryl benzene sulfonate were less than yields of runs #4 and #5, in which all of the asks were maintained at a. temperature within the range about 100 to about C. For obtaining the least kerosenelike odor, a chlorlnating temperature in the upper part of the temperature range about 100 be used to equal advantage. For example, apparatus made from a nonresistant metal and lined with vitreous enamel, or other resistant material could be used. I

' Furthermore, itis not intended to limit the invention to processes ofchlorination carried out at atmosphericpressure as the pressure within the apparatus may be greater or less than atmospheric without going outside vthe scope of the to.4 7 5 present invention. llifor examplam superatmos-` 2i pheric pressure may be used .at elevated tempera'- tures such that lower-boiling constituents of the hydrocarbon mixture would vaporize at atmospheric pressure.

Due to the limited solubility of chlorine gas in petroleum hydrocarbons, cincient operation of a continuous chlorination process makes it highly desirable to provide some means of insuring intimate contact between the stream of chlorine gas and the stream of hydrocarbon fraction. Various nozzles can be used for the chlorine inlets employed in accordance with my invention. For example,- the chlorine may be fed through a glass capillary or through a sintered 'glass filter or through a closed pipe having a number of small openings at the closed end or through a porous ceramic ware inlet, such asl an alundun'i cup or disc. In any case, lit is preferred to contactntli chlorine with the kerosene lin such a way that the mingling of the chlorine with the' kerosene is effected with greatest possible speed and completeness. Various devices other than' those de;

scribed are' well known to those skilled in the art.

While the preferred embodiment ofthe invention involves the introduction of chlorine into a flowing stream of the hydrocarbon mixture, it not essential that the initial chlorination to the limited extent be carried out in this mannerA Thus, the initial chlorination may be carried out in a static body of hydrocarbon mixture (for ex ample, in one of several alternate tanks of hyldrocarbon mixture from' which the partially chlorinated hydrocarbon mixture is charged to the subsequent chlorinators), particularly in-connec@ tion with the initial chlorination of a-hydrocarbon mixture by residual chlorine contained in hydrogen chloride exit gases from a lsubsequent. stage of chlorination.

The invention furthermore is not limited to treatment of the aromatic compounds disclosed in the above examples but may be employed in connection with the manufacture of other alkyl aromatic sulfonates and especially those of monoand di-nuclear aromatic hydrocarbons and their simple unsulfonated substitution products. amples of such compounds are benzene, toluene, naphthalene, diphenyl, phenol, cresol, anisole, phenetole and naphthol. Benzene is preferred.

The yield of desirable alkyl aromatic sulfonates is greatly influenced by the proportion of chlorinated petroleum fraction employed with respect to the amount of aromatic hydrocarbon or iinsulfonated derivative thereof used in the preparation of the alkylated aromatic compounds. Theoretically, in order to obtain complete reaction one mol of aromatic compound must be used per atom of chlorine combined with the petroleum hydrocarbon fraction. In practice an amount of aromatic compound in large molecular excess, preferably about twice the weight of chlorinated petroleum is used, as this favors complete reaction of the chlorinated petroleum with the aromatic body, and permits less decomposition and lindesirable tay-products in the condensation reaction. The improved results of the present invention are best eiected by a condensation of the chlo'- rinated hydrocarbon and aromatic compound with an amount of anhydrous aluminum chloride which is from 1 to 8 per cent of the weight of chlorinated hydrocarbon charge; a better 'and preferable proportion is from 2 per cent to 5 per cent. In general, with amounts less than 2 per cent, condensation is retarded, while with amounts larger than 5 per cent there is no marked increase in the rate of condensation and EX- i per cent oleum, and chlor-sulfonic acid may be; used as sulfonating' agents. The sulfonation may be carried out in the presence of inert solvents or diluents, and sulfonation assistants as, for eXamv ple, the lower fatty acids and their anhydrldes,r

such as acetic acid and acetic anhydride, or the alkali metal sulfates, such as sodium or potas sium sulfate, may be employed. Also, the temperature at which the sulfonation is carried outv may vary within wide limits. For example, temperatures as low as about 0 C. and as high-asv about 140 C. maybe employed. In generali, the more vigorous the' sulfonating agent the lower is the preferred temperature. In most cases the sulfonation is carried out most eflieiently at temperatures between 5 and 90 C. For complete Sulfonation the sulfonating agent in terms of 100.per cent sulfuric acid may be employed in amounts4 which 'range from 0.3 to 5 times or morev the weight of the condensation product to be sulfof nated. Ordinarily, the extent to-which the sul-v fonation is carried out will vary with the indi* vidual material being sulfonated, the duration of.

the sulfonation, and the use to be made of the sulfonated product. Monosulfonation is preferred.

The alkyl aromatic sulfonates may be prepared in the form of their free sulfonic acids or in the form of their salts. Thus they may bewprepared in the -form of their alkali metal, alkaline earth metal,- ammonium, or organic base salts .(e. g.,

amine salts). They are of particular value in thel form of their alkali metal and especially sodium salts.

Since certain changes may be made in the proc ess described above without departing from the scope of the invention, it will be understood that.

the description should be interpreted as illustra tiv'e and not in a limiting sense.

This application is a continuation-impart of,l

my application Serial No. 400,334, led June 28, 1941.

I claim:

l. The method of chlorinating a hydrocarbon mixture of the type of a petroleum distillate boil ing over a temperature range lying between 80 C. at atmospheric pressure and 350 C. at 22 mm. absolute pressure, which comprises introducing chlorine gas into the hydrocarbon mixture in,

hquid phase in an amount not exceeding that er fective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination, and introducing additional chlorine gas into a flowing stream of the resulting partially chlorinated hydrocarbon mixture while maintaining the temperature of the reaction mixture within the range 60 to 175 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being at least suiiicient to result in a' chlorinated hydrocarbon mixture chlorinated to a degree corresponding to chlorination. whereby a chlorinated hydrocarbon mixture having a low aniline point is obtained.

2. The method of chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling over atemperatur'e range lying between 80 Cl 7s at atmospheric pressure and 350 C. at 22 anni...

drocarbon mixture employed being at least suf-v ficient to result in a chlorinated hydrocarbonv mixture chlorinated to a degree correspondingto 75% chlorination, whereby a chlorinated hydrocarbon mixture having a low aniline point is obtained.

3. The method of chlorinating a, hydrocarbon mixture of the type of a petroleum distillate boiling for the most part over a temperature range', lying between 180 and 300 C. at atmospheric pressure, which comprises introducing chlorinev gas into the hydrocarbon mixture in liquid phase in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree corresponding to chlorination while maintain-- ing the temperature of the reaction mixture within the range 80 to 155 C, and introducing additional chlorine gas at a gage pressure not exceeding 25 pounds per square inch into a owing stream of the resulting partially chlorinated hy-A drocarbon mixture while maintaining the temperature of the reaction mixture Within Athe range 80 to 155 C., the total amount of chlorine relal chlorination zone, introducing chlorine gas at a gage pressure not exceeding 25 pounds per square inch into the hydrocarbon mixture in said zone in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination while in said zone, and introducing additional chlorine gas at a gage pressure not exceeding 25` pounds per square inch into a flowing stream of the resulting partially chlorinated hydrocarbon mixture while maintaining the temperature of the reaction mixture within the range'80 to 155 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being suflicient to result in a chlorinated hydrocarbon ixture chlorinated to a degree corresponding to at least 75% but not more than 200% chlo ination, whereby a chlorinated hydrocarbon mixture having a low aniline point is obtained.

5. The method of chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling over a temperature range lying between 80 C. at atmospheric pressure and 350 C. at 22 mm. absolute pressure, which comprises owing a tion zones, introducing chlorine gas into the owing hydrocarbon mixture in said zones, the total amount of chlorine introduced relative to the amount of hydrocarbon mixture being such that the resulting chlorinated hydrocarbon mixture contains an amount of chlorine corresponding to more than 100% chlorination, limiting the amount of chlorine introduced into the hydrocarbon mixture in the rst chlorination zone to such an extent that the chlorinated hydrocarbon mixture produced in said zone contains an amount of or ganically combined chlorine not exceeding that corresponding to 15% chlorinationl and introducing additional chlorine gas into the resulting partially chlorinated hydrocarbon mixture in at least one zone While maintaining the temperature of the reaction mixture Within the range 60 to 175 C., whereby a chlorinated hydrocarbon 5-,

ture having a low aniline point is obtained.

6. The method of chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling for the most part over a temperature range lying between 180 andl 300 C. at atmospheric pressure, which comprises flowing a stream of the hydrocarbon mixture in liquid phase through a chlorination zone, introducing chlorine gas at a gage pressure not exceeding 25 pounds per square inch into the hydrocarbon mixture in said zone stream of the hydrocarbon mixture in liquid.

in an amount not exceeding that elective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination while in said zone, and flowing a stream of the resulting partially chlorinated hydrocarbon mixture in liquid phase through at least one additional chlorination zone, at an average velocity of to 20,000 feet per hour while introducing additional chlorine gas at a gage pressure not exceeding 25 pounds per square inch and while maintaining the temperature of the reaction mixture Within the range to 155 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being suflicient to result in a chlorinated hydrocarbon mixture containing an amount of organically combined chlorine corresponding to to 200% chlori tion, whereby a chlorinated hydrocarbon mixt re having a low aniline point is obtained.

7. The method of chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling for the most part over a temperature range' the hydrocarbon mixture in said zone in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree corresponding .to 15% chlorination while in said zone, and owing a stream of the resulting partially chlorinated hydrocarbon mixture in liquid phase through at least one additional chlorination zone, at an average velocity of 50 to 20,000 feet per hour while introducing additional chlorine gas and while maintaining the temperature of the reaction mixture within the range to 155 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being sulcient to result in a chlorinated hydrocarbon mixture containing an amount of organically combined chlorine corresponding to more than 100% but not more than 150% chlorination, whereby a chlorinated hydrocarbon mixture having a. low aniline point is obtained.

8. The method of chlorinating a hydrocarbon mixture 'of thetype of a. petroleum distillate boil-av ing for the most part over a temperature range lying between 180 and 300 C. at atmospheric pressure, which comprises ilowing a stream of the hydrocarbon mixture in liquid phase through a chlorination zone, introducing chlorine gas into the hydrocarbon mixture in said zone in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination while in said zone, and flowing a stream of the resulting partially chlorinated hydrocarbon mixture in liquid phase through at least one additional chlorination zone, at an average velocity of 50 to 1000 feet per hour while introducing additional chlorine gas and while maintaining the temperature of the reaction mixture within the range 100 to 155 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being suiicient to result in a chlorinated hydrocarbon mixture containing an amount of organically combined chlorine corresponding to more than 100% but not more than 200% chlorination, whereby a chlorinated hydrocarbon mixture having a loW aniline point is obtained.

9. The method oi chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling for the most part over a temperature range lying between 180 and 300 C. at atmospheric pressure, which comprises flowing a stream of the hydrocarbon mixture in liquid phase, maintained at a temperature within the range 60 to 175 C., through a chlorination zone, introducing chlorine gas into the hydrocarbon mixture in said zone in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination while in said zone, and flowing a stream of the resulting partially chlorinated hydrocarbon mixture in liquid phase through at least one additional chlorination zone of greater length than the eiective average -ff width of the stream, at an average velocity of 50 to 5000 feet per hour While introducing additional chlorine gas and while maintaining the temperature of the reaction mixture within the range 100 to 175 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being suicient to result in a chlorinated hydrocarbon mixture containing an amount of organically combined chlorine corresponding to at least 757(l but not more than 200% chlorizfation, whereby a chlorinated hydrocarbon mix ure having a low aniline point is obtained.

10. The method of chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling for the most part over a temperature range lying between 180 and 300 C. at atmospheric pressure, which comprises flowing a stream of the hydrocarbon mixture in liquid phase maintained at a temperature Within the range 60 to 175 C., through a chlorination zone, introducing chlorine gas at a gage pressure not exceeding 25 pounds per square inch into the hydrocarbon mixture in said zone in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination while in said zone, and llowing a stream of the resulting partially chlorinated hydrocarbon mixture in liquid phase through at least one additional chlorination zone, at an average velocity of 50 to 600 feet per hour while introducing additional chlorine gas at a gage pressure not exceeding 25 pounds per square inch and while maintaining the temperature of the reaction mixture within the range 110 to 155 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being sutcient to result in a chlorinated hydrocarbon mixture containing an amount of organically combined chlorine corresponding to more than but not more than chlorination, whereby a chlorinated hydrocarbon mixture having a low aniline point is obtained.

11. The method of chlorinating a kerosene fraction of a petroleum distillate of the Pennsylvania petroleum type, which comprises flowing a stream of the kerosene in liquid phase through a chlorination zone, introducing chlorine gas into the kerosene in said zone in an amount not exceeding that eiective to chlorinate the kerosene to a degree corresponding to 15% chlorination while in said zone, and flowing a stream of the resulting partially chlorinated kerosene in liquid phase through at least one additional chlorination zone of greater length than the effective average width of the stream, at an average velocity of 50 to 5000 feet per hour while introducing additional chlorine gas at a gage pressure not exceeding 25 pounds per square inch and while maintaining the temperature of the reaction mixture Within the range'llO" to 155 C., the total amount of chlorine relative to the amount of kerosene employed being sufficient to result in a chlorinated kerosene containing an amount of organically combined chlorine corresponding to more than 100% but not more than 1 chlorination, whereby a chlorinated ker ene having a low aniline point is obtained.

12. In the manufacture of alkyl aromatic sulfonates by chlorinating a hydrocarbon mixture of the type of a. petroleum distillate boiling over a temperature range lying between 80 C. at atmospheric pressure and 350 C., at 22 mm. absolute pressure condensing a resulting mixture of chlorinated hydrocarbons with an aromatic compound. and sulfonating a resulting mixture o1' alkyl aromatic com-pounds, the improvement which comprises flowing a stream of the hydrocarbon mixture in liquid phase through a chlorination zone, introducing chlorine gas into the hydrocarbon mixture in said zone in an amount not exceeding that eiective to chlorinate the hydrocarbon mixture to a degree corresponding to 15% chlorination while in said zone, and introducing additional chlorine gas into a flowing stream of the resulting partially chlorinated hydrocarbon mixture while maintaining the temperature of the reaction mixture within the range 60 to 175 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being at least sufficient-'to result in a. chlorinated hydrocarbon mixture/ chlorinated to a degree corresponding to 75% chlorination.

13. In the manufacture of alkyl sulfonates by chlorinating a hydrocarbon mixture of the type of a petroleum distillate boiling over a temperature range lying between 80 C. at atmospheric pressure and 350 C., at 22 mm. absolute pressure, condensing a resulting mixture of chlorinated hydrocarbons with an aromatic compound, and sulfonating a, resulting mixture of alkyl aromatic compounds, the improvement which comprises flowing a stream of the hydrocarbon mixture in liquid phase through a chlorination zone, introducing chlorine gas into the hydrocarbon mixture in said zone in an amount not exceeding that effective to chlorinate the hydrocarbon mixture to a degree'corresponding to 15% chlorination While in said zone. and flowing a stream of the resulting chlorinated hydrocarbon mixture in liquid phase through at least one additional chlorinature of the reaction mixture within the range 82'* t 155 C., the total amount of chlorine relative to the amount of hydrocarbon mixture employed being sufiicient to result in a chlorinated hydrocarbon mixture containing an amount of organi- ,cally combined chlorine corresponding to more than 100% but not more than 200% chlorination. 14. In the manufacture of alkyl benzene sulfonates by chlorinating a kerosene fraction of a petroleum distillate of the Pennsylvania petro- .leum type, condensing the resulting chlorinated kerosene with benzene, and sulfonating the resulting mixture of alkyl benzenes, the improvement which comprises ilowing a, stream of the kerosene in liquid phase through a chlorination zone, introducing chlorine gas into the hydrocarbon mixture in said zone in an amount not exceeding y that eiective to chlorinate the hydrocarbon mixture to a degree corresponding to chlorination while in said zone, and iiowing a stream of the resulting partially chlorinated hydrocarbon mixture in liquid phase through at least one addi- Ltional chlorination zone of greater length than 'the effective average width of the stream, at au .average velocity of to 5000 feet per hour while introducing additional chlorine gas and whilemaintaining the temperature of the reaction mixture within the range 100 to 155 C., the total amount of chlorine relative to the amount of hy drocarbon mixture employed being suilicient to .result in a chlorinated hydrocarbon mixture containing an amount of organically combined chierine corresponding to atleast but not more than 150% chlorination. n

15. In the manufacture of alkyl benzene sulfonates by chlorinating a kerosene fraction of a petroleum distillate of the Pennsylvania petro- 28 leum type, condensing the resulting chlorinated kerosene with benzene, and sulfonating the resulting mixture of alkyl benzenes, the improvement which comprises flowing a stream of the kerosene in liquid phase through a chlorination zone, introducing chlorine gas into the kerosene in said zone in an amount not exceeding that effective to chlorinate the kerosene to a degree corresponding to 15% chlorination while in said zone while maintaining the temperature of the reaction mixture within the range to 155 C., and ilowing a stream of the resulting partially chlorinated kerosene in liquid phase through at least one additonai chlorination zone, at an average velocity of 50 to 600 feet per hour while introducing additional chlorine gas at a gage pressure not exceeding 25 pounds per square inch and while maintaining the temperature of the reaction mixture within the range 110 to 155 C., the total amount o chlorine relative to the amount of kerosene employed being sufficient to result in a chlorinated kerosene containing an amount of organically combined chlorine corresponding to more than but not more than 150% chlorination.

LAWRENCE H. FLEII.

REFERENCES CITED The following references are of record in the le oi this patent:

UNITED STATES PATENTS Number Name Date 1,224,485 Mesereau May 1, 1917 1,432,761 Koch Oct. 24, 1922 2,022 619 Galsworthy Nov. 26. 1935 2,105,733 Hass et al. Jan. 18, 1938 2,147,577 Hass et al. Feb. 14, 1939 2,220,099 Guenther et al Nov. 5, 1940 2,247,365 Flett July 1, 1941 

15. IN THE MANUFACTURE OF ALKYL BENZENE SULFONATES BY CHLORINATING A KEROSENE FRACTION OF A PETROLEUM DISTILLATE OF THE PENNSYLVANIA PETROLEUM TYPE, CONDENSING THE RESULTING CHLORINATED KEROSENE WITH BENZENE, AND SULFONATING THE RESULTING MIXTURE OF ALKYL BENZENES, THE IMPROVEMENT WHICH COMPRISES FLOWING A STREAM OF THE KEROSENE IN LIQUID PHASE THROUGH A CHLORINATION ZONE, INTRODUCING CHLORINE GAS INTO THE KEROSENE IN SAID ZONE IN AN AMOUNT NOT EXCEEDING THAT EFFECTIVE TO CHLORINATE THE KEROSENE TO A DEGREE CORRESPONDING TO 15% CHLORINATION WHILE IN SAID ZONE WHILE MAINTAINING THE TEMPERATURE OF THE REACTION MIXTURE WITHIN THE RANGE 80* TO 155*C., AND FLOWING A STREAM OF THE RESULTING PARTIALLY CHLORINATED KEROSENE IN LIQUID PHASE THROUGH AT LEAST ONE ADDITIONAL CHLORINATION ZONE, AT AN AVERAGE VELOCITY OF 50 TO 600 FEET PER HOUR WHILE INTRODUCING ADDITIONAL CHLORINE GAS AT A GAGE PRESSURE NOT EXCEEDING 25 POUNDS PER SQUARE INCH AND WHILE MAINTAINING THE TEMPERATURE OF THE REACTION MIXTURE WITHIN THE RANGE 110* TO 155*C., THE TOTAL AMOUNT OF CHLORINE RELATIVE TO THE AMOUNT OF KEROSENE EMPLOYED BEING SUFFICIENT TO A RESULT IN A CHLORINATED KEROSENE CONTAINING AN AMOUNT OF ORGANICALLY COMBINED CHLORINE CORRESPONDING TO MORE THAN 100% BUT NOT MORE THAN 150% CHLORINATION. 